Photographic silver halide material containing disazo dyes for the silver dyestuff bleaching process

ABSTRACT

A photographic light-sensitive material, especially for the silver dyestuff bleaching process is provided, which contains on a support in at least one layer, at least one dyestuff of the formula   IN WHICH R1, R2, D and E are organic radicals, R1 and R2 being in the 3-, 4- or 5-positions to the -CO-group, K is an acyl radical and m, n and p each equals 1 or 2. These dyestuffs are resistant to diffusion, form stable aqueous solutions, can be easily bleached, are fast to light and have favourable spectral properties.

United States Patent [191 Stauner et al.

[ Aug. 28, 1973 PHOTOGRAPIIIC SILVER IIALIDE MATERIAL CONTAININGDISAZO'DYES FOR THE SILVER DYESTUFF BLEACI-IING PROCESS [75] Inventors:Thomas Stauner, Marly-le-Grand;

Bernhard Piller, Marly-le-Petit; Alfred Froehllch, Marly-le-Grand, all

of Switzerland [73] Assignee: Ciba-Geigy AG, Basel, Switzerland [22]Filed: Dec. 30, 1971 [21] Appl. No.: 214,456

Related US. Application Data [63] Continuation of Ser. No. 18,311, March[0, 1970,

abandoned.

[30] Foreign Application Priority Data Primary ExaminerNorman G. TorchinAssistant Examiner-Richard L. Schilling Attorney-Harry Goldsmith et al.

[5 7 ABSTRACT A photographic light-sensitive material, especially forthe silver dyestuff bleaching process is provided, which contains on asupport in at least one layer, at least one dyestufi of the formula inwhich R,, R,, D and E are organic radicals, R, and R, being in the 3-,4- or 5-positions to the CO- group, K is an acyl radical and m, n and peach equals 1 or 2. These dyestuffs are resistant to diffusion, formstable aqueous solutions, can be easily bleached, are fast to light andhave favourable spectral properties.

17 Claims, No Drawings 1 2 PHOTOGRAPIIIC SILVE HAL D M TERI L wherein Dand E independently of one another CONTAINING DISAZO DYES OR THE S LVEReach denotes a methyl, methoxy, ethoxy or hydroxye- DYES U F BLEACIIINGPROCESS thoxy group and R,, R,, K, m, n and p have the significanceindicated. Thls a commuatlon of apphcanon 18,31 5 Particularly suitabledyestuffs correspond to the for- This invention provides photographiclight-sensitive wherein R denotes a hydrogen or halogen atom or amaterial, especially for the silver dyestuff bleaching nitro group, R,denotes a halogen atom, a nitro, cyano, process, which contains on asupport in at least one trifluoromethyl, lower alkyl or alkoxy group ora resilayer, at least one dyestuff of the formula due of the formulaNl-lCO-X,, NH-SO Y,, n a R1 g 0 0-NElI 11 E H0 HN-K R2 =N -N=N H(O;S),,i SO;H D HOaS- (SOa)(m-i)(p-1)I I oak- Z)(2-m)(v-U wherein R denotes ahalogen atom, anitro, cyano, tri- 3O -SO,--Z, or COW,, in which Xrepresents an fluoromethyl, lower alkyl or alko ry group or a residueHOOC-alkyl, HOOC-alkenyl, HOOC-phenyl or phenyl of the formula Nl-l-COX,NHSO,-Y, group, Y, represents a lower alkyl or alkylphenyl group SO,-Zor CO-W, in which X represents a hyor a phenyl group, 2 represents alower alkyl, phenyl droxyl, HOOC-alkyl, l-IOOC-alkenyl, HOOC-phenyl, orsubstituted or unsubstituted amino group and W HO S-phenyl, phenyl,furyl, thienyl or pyridyl group, Y 35 represents a lower alkyl or alkoxygroup or a phenyl or represents a lower alkyl or a phenyl, alkylphenylor hydroxyl group, and K, m, n and p have the significance HOOC-phenylgroup, Z represents a hydroxyl, lower indicated, and R, and R, are inthe 3-, 4- or 5-positions alkyl, phenyl or a substituted orunsubstituted amino to the CO- group.

group and W represents a lower alkyl or alkoxy group, Good results arealso obtained with dyestuffs of the or a hydrowyl, phenyl or substitutedor unsubstituted 40 formula DUO-HN OH E HO 11111-1; R6

N=N N=N amino group, R denotes a hydrogen atom or has the wherein Rdenotes a halogen atom, a nitro, trifluorosignificance indicated for RR, and R, being in the 3-, methyl, lower alkyl or alkoxy group, or aradical of the 4- or S-positions to the C0 group, D and E indeformulaNl-l-CO-X, Nl-lSO,-Y, SO,-Z, pendently of one another each denotes ahydrogen or or -C0W,, in which X represents a hydroxyl, chlorine atom ora methyl, methoxy, ethoxy or hydrox- HOOC-alkyl, HOOC-alkenyl,HOOC-phenyl, H0 8- yethoxy group, K denotes an acyl radical of analiphatic 55 phenyl, phenyl, furyl, thienyl or pyridyl group, Y repreoraromatic carboxylic or sulphonic acid which may be sents a lower alkylor a phenyl, alkylphenyl or HOOC- further substituted, or of aheterocyclic carboxylic phenyl group and Z, represents a hydroxyl, loweralkyl acid, and m, n and p each equals 1 or 2. or a substituted orunsubstituted amino group, W

Preferred dyestufis correspond to the formula represents a lower alkylor alkoxy group or a phenyl or hydroxyl group R denotes a hydrogen atomor has the E W X, Y, K, m and n have the significance indisignificanceindicated for R R and R being in the 3-, caled, 0 5-P to the g p, D andE inde- The lower alkyl or alkoxy radicals in R,, R R R Pendemly 0f oneanQther each denotes a y g or R and R are preferably those having atmost 5 carbon C e atom a y y, h xy 0r hydrox- 5 atoms. Similarly, thealkyl or alkenyl radicals in X or X yethoxy group,Kdenotes an acylradical of an aliphatic and Y or Y preferably contain at most fivecarbon or aromatic carboxylic or sulphonic acid which may be atoms.further substituted or of a heterocyclic carboxylic acid, Dyestuffs ofthe formula ;g COHI lI (|)H ()OHQ Htl) 1TIH-K N=N -N=N H(0z )n-i -so31100113 H038 '-(s J)ml (S 03) 1 II (S O (OZ-r11 and and P each equals 1 ofwherein R R,,, K, n and m have the significance indi- Photographicmaterial of special interest contains a cated, are referentially d,dyestuff 0f t formula Photographic material which contains at least one@CO-NH OH E, H0 HIIIK R5 I -N:N- N=N moss)- SO3I-I 1)! 11035- 3)ml (sOm-nH (S 3)(1m) wherein Rhd 5, R D E,, K, m and n have thesignifidyestuff of the formula 8) R5 m m -c o-nN on 0on3 ml) lTII[-l{}I03S -s 0311 (i)CH3 Hols -s0.ur

cance indicated. I wherein R R and K have the significance indicated,

The radicals D and E and/or D and E,, where they is particularlyadvantageous. do not represent hydrogen atoms, are preferably in theAmongst the dyestuffs of formulae (6) and (8), those paraposition to oneanother. 40 of the formula (9) fi; m

g2 HN OH (30113 HO NH-K I N=N H035 S0;H OCH; HOgS- $0311 Very suitabledyestuffs of formulae (3 and (5) are wehrein R;,, R, and K have thesignificance indicated, those of the formula v, should be particularlyemphasised. (6) R3 0 ONH OH I JI Hp I|1NK R1 N=N N=N H(03s)., 1 sour 1),Hols so3)m H sonhu Oa)(2-m)H wherein R denotes a halogen atom, a nitro,trifluoro- Dyestuffs of the formula (9) with a preferred acyl methyl,lower alkyl or alkoxy group or a radical of the radical K correspond tothe formula 10) Ra I CO--H1TI on mm ml) slur-Kl R7 N=N- N=N H038 SO3HOCH; HO3S sour formula Nl-l-COX, NHSO Y, SO Z wherein K denotes the acylradical of an alkanecaror CO-W,, wherein Z represents a lower alkyl orboxylic acid having preferably at most 6 carbon atoms, substituted orunsubstituted amino group, and R D,, a substituted or unsubstitutedbenzene carboxylic or pyridine carboxylic acid or a substituted orunsubstituted benzene sulphonic acid, and R and R have the significanceindicated.

Advantageous results are obtained when using dyestuffs of the formuladine carboxylic acid, and R, and R, have the signifi- *COHN OH win no Il I n cance indicated.

Photographic material which contains at least one dyestuff of theformula g2 0 OIIN OH OCH: HO Rn l l HOaS- SO3H OCHa HOJS wherein Rdenotes a chlorine or bromine atom, a ni- 6-0 0- or H 0 0 0-0-0 O--NHgroup,

R denotes a hydrogen or chlorine atom, the radicals R and R being in the3- and 4-positions to the CO 60 group, and K represents the acyl radicalof pyridine-3- carboxylic acid or of a benzene carboxylic acid of the 5E C 0-1117 (Hi I i i Rm (i3.

formula C 0 X G: wherein G, denotes a hydrogen or halogen atom, espe-HOaS- cially a chlorine or bromine atom, and G, denotes a hydrogen orhalogen atom, especially a chlorine or bro- 15 mine atom, or a nitro,trifluoromethyl or Z -SO,--

group, wherein 2,, represents a lower alkyl or substituted orunsubstituted amino group. Preferably, the lower alkyl group in Z, is amethyl radical.

in particular, however, dyestuffs of the formula wherein K representsthe acyl radical of pyridine-3- carboxylic acid or of a benzenecarboxylic acid of the 30 formula NH-Ks wherein G; denotes a hydrogen orchlorine atom and 6, denotes a hydrogen or chlorine atom or a nitro,trifluoromethyl or H,NSO,group and R and R, have the significanceindicated, are of particular interest.

Amongst the dyestuffs of formula (13), those of the formula OCH; lIOIIIH-Jis HOzS -s0=11 OCII; IIOaS SO H wherein R,,, denotes a chlorineatom, a nitro group or a H NSO,group and R, and K have the significanceindicated and the radicals R and R are in the 3- and 4-positions to theCO group, are preferred.

Particularly advantageous results are obtained by using dyestuffs of theformula OCH; lIO

wherein G denotes a hydrogen or chlorine atom and alkaline earth metalgroup or especially the alkali metal G denotes a hydrogen or chlorineatom or an group or ammonium. H NSO group, and R and R have the signifi-The radicals cance indicated. in

Amongst the dyestuffs of formula (3), those of the 5 2 -cformula R:

-c o-HN (1)11 0on3 ml) NIL-Ks H038 -s0irI ot sn 1103s SOZII should beemphasised, wherein R represents a chloin the dyestuffs of formula (I)may for example be derine or bromine atom or a cyano, a nitro,trifluororived from the following acids or halides! meth l, H N S0 H CNH. SO H C SQ nitrobenzoic acid, 3-nitrobenzoic acid, 4-

H5C8 SQ2 H3C SO2 NH HSCG SO2 NH chlorobenzoic acid, 3-chlorobenzoicacid, 3,4- dichlorobenzoic acid, 4-bromobenzoic acid, 3-triacid,3-toluic acid, 4-toluic acid, 4-fluorobenzoic acid,

H C CONH--, H C CO--, HOOC(CH 4-t-butylbenzoic acid,4-chloro-3-methylbenzoic acid,

) -CONl-l--, HOOC(CH CONH, HOO- 4-chloro-3-nitrobenzoic acid,3-methoxy-4- CCl-l=CH-CONH, HOOC, H CO--, nitrobenzoic acid,3-sulphamoylbenzoic acid, H COOC, 3-methylsulphamoylbenzoic acid, 4-sulphamoylbenzoic acid, 4-chloro-3- 004* o HO0 C -C0NII gro p.sulphamoylbenzoic acid, 4-chloro-3-methylsulphamoylbenzoic acid,3-methylsulphonylbenzoic acid, R represents a nitro group or a hydrogenor chlorine 4-m th l l h lb i id 4- atom and K represents the acylradical of pyridine-3- benzoylaminobenzoic acid and4-chloro-3-methylsulcarboxylic acid, benzene sulphonic acid or a benzenephonylbenzoic acid. carboxylic acid of the formula The radical K in thedyestuffs of formula 1) may for (ma) example be derived from thefollowing acids or their halides: 4-chlorobenzoic acid, 3-chlorobenz0icacid, D 2-chlorobenzoic acid, 4-nitrobenzoic acid, 3- nitrobenzoic acid,2,4-dichlorobenzoic acid, 2,5- wherein G denotes a hydrogen or chlorineatome and dichlorobenzoic acid, 3,4-dichlorobenzoic acid, 4- G, denotesa hydrogen or chlorine atom, or a nitro, trichloro-3-nitrobenzoic acid,2-chloro-4-nitrobenzoic fluoromethyl, H CSO or H N-SO, group. acid,3-trifluoromethylbenzoic acid, 4-tri- Advantageous results areparticularly obtained with fluoromethylbenzoic acid, 3-toluic acid,4-toluic acid, dyestuffs of the formula 4-fluorobenzoic acid,4-acetylaminobenzoic acid, 3-

R9 G3 g5 COHN 0H 0 3Hi Ho 1-|IIIC0@ R10 1 I wherein R,,, G, and 6,, havethe significance indicated acetylaminobenzoic acid, 4-methoxybenzoicacid, and R denotes a chlorine or bromine atom or a nitro, hl r-4-meth0xybenz0ic acid, 3methoxy-4- H NSO,-, H C-SO,, H COOC--, H,CSO-nitrobenzoic acid, 3,5-dimethoxybenzoic acid, 3- NH or NC groupmethoxybenzoic acid, 4-chloro-3-methylbenzoic acid,

The dyestuffs of formulae (l6) and (17) include very 3-sulphamoylbenzoicacid, 4-sulphamoylbenloic acid, suitable cyan dyestuffs, which forexample correspond 4-chl0r0-3-sulpham0ylbenz0i acid, to formulae (101)to (109) and to of methylsulphamoylbenzoic acid, S-methylsulphamoyl- Tbl I h i ft benzoic acid, 4-methylsulphonylbenzoic acid, 4- Thedyestuffs of formulae (1) to (17) cannot only be hl0r0- y p y acid, inthe form of their free acids as indicated, that is to say bromobenzoic a3-bromobenzoic acid, nicotinic having HOOC or HO S groups, but also assalts. acid, isonicotinic acid, pyridine-Z-carboxylic acid, ben-Depending on the conditions under which the d estuff zoic acid,4-t-butyl-benzoic acid, 4-acetylbenzoic acid,

is separated, for example on the chosen pH value or on4-meth0xycarb0nylbenz0ic a id, 3- the cation which is present in thesalt used for separatsuccinylaminobenzoic acid, 4-succinylaminobenzoicing, the acid groups can be in the form of SO or 65 acid,3-glutarylamin0benz0ic acid, COOcation groups, for example SO Na,glutarylaminobenzoic acid, 3-fumaroylaminobenzoic SO K, (-SO Ca,--COONa, COOLi and acid, 4-fumaroylaminobenzoic acid, 3-

COONH that is to say, preferably with salts of thebenzenesulphonylaminobenzoic acid,

benzenesulphonylaminobenzoic acid, 3- tosylaminobenzoic acid,4-tosylaminobenzoic acid, 3methylsulphonylaminobenzoic acid, 4methylsulphonylaminobenzoic acid, 3- furoylaminobenzoic acid,4-furoylaminobenzoic acid, 3-pyridoylaminobenzoic acid,4-pyridoylaminobenzoic acid, 3-thenoylaminobenzoic acid and 4-thenoylaminobenzoic acid.

The radicals -SO,Y or SO,Y in the radicals NHSO Y or NHSO Y, which occuras substituents R R and R R and R may for example be derived from thefollowing acids or their halides: methane sulphonic acid, benzenesulphonic acid, 4-methylbenzene sulphonic acid or 3-sulphobenzoic acid.

The radicals COX or -COX in the radicals NHCOX or ---NHCOX which occuras substituents R R R,,, R and R may for example be derived from thefollowing acids or succinic halides or anhydrides: formic acid, maleicacid, fumaric acid, succinis acid, glutaric acid, benzoic acid,terephthalic acid, isophthalic acid, 3-sulphobenzoic acid, furane-2-carboxylic acid, thiophene-Z-carboxylic acid and pyridine-2-, -3- and-4-carboxylic acid.

The radicals may for example be derived from the following amines:

1-amino-2,3 -dimethoxy-4-nitrobenzene, l-amino-2,5-dimethoxy-4-nitrobenzene, l-amino-2,6-dimethoxy-4- nitrobenzene,l-amino-2-chloro-5 -methoxy-4- acetylaminobenzene, l-amino-2-methoxy-4-nitrobenzene, l-amino-2-hydroxyethoxy-4- nitrobenzene, lamino-2,5-dimethoxy-4- acetylaminobenzene, l-amino-2 ,5 -dimethoxy-4-formylaminobenzene, l-amino-2 ,5-dimethoxy-4- formylaminobenzene, 1-amino-2-chloro-4- nitrobenze ne, 1-amino-3-chloro-4-nitrobenzene, 1-amino-2-methyl-4-nitrobenzene, l-amino-2-ethoxy-4- nitrobenzene,l-amino-2-chloro-5 -methyl-4- acetylaminobenzene 1-amino-2-methyl-5-chloro-4- nitrobenzene, 1-amino-2-chloro-5 -methyl-4-acetylaminobenzene, l-amino-Z-chloro-S-hydroxyethoxy-4-acetylaminobenzene, 1 -amino-2- methyl-5 -methoxy-4-nitrobenzene, 1-amino-2- methoxy-S-chloro-4-nitrobenzene,1-amino-2- methoxy5 -methyl-4-nitrobenzene, 1 -amino-2-methoxy-5-hydroxyethoxy-4-nitrobenzene, l-amino-2-hydroxyethoxy-5-chloro-4-nitrobenzene, 1-arnino-2- hydroxy-ethoxy-S-methyl-4-nitrobenzene, l-amino- 2,5-diethoxy-4-nitrobenzene andl-amino-2,5-

dichloro-4-nitrobenzene.

The dyestuffs of formula (1) can be manufactured according to variousknown processes. Thus an amine XC ONHQ'C 0-411 (HI E HQNQN 0 D whereun Ldenotes a protective group which can be split off, and D and E have thesignificance indicated, may be diazotised and coupled with al-acylamino-S- hydroxynaphthalene disulphonic acid of the formula gCO-HN OH of the formula or the formula (20 HO NH-K wherein K, m, n and phave the significance indicated. Similarly, an amine of formula (18a) or(18b) may be diazotised and coupled with the compound of formula (20)and after reduction of the nitro group to the amino group or splittingoff the protective group and further dizotisation, the aminoazo dyestuffthus obtained is coupled with the compound of formula (19).

In the synthesis of dyestuffs having NO,- or SO,N- H, groups in R Rand/or K, for example dyestuffs of formulae (101) to (105), (107) to(110), (113), (115), (116), (119), (120), to (127) and (129) givenbelow, it is advantageous first to manufacture the aminomonoazo dyestuffwhich is free from such groups, for example those of the formulae (2.3),(2.4) and (2.8) given below, andthen diazotise and couple it with thesecond coupling component containing N0 or SO,NH, groups, for examplethose of the formulae (1.3), (1.4), (1.8), (1.32) or (1.33) given below.

Dyestuffs having the radicals NH COX or -NYSO,Y in R or K, wherein X andY have the significance indicated, for example those of the formula ak-(e-m) (iv-D H 12 wherein X, R,, E, D, K, m, n and p have the si nifitrasonics can also be employed. The dyestuff may also indicated, canalso be manufactured by first synthesisbe a de in the So d form Or as apaste nstead Of n 50- ing a dyestuff of the formula lution. (272) II Nco HN OH 7 F i if 15 K 3 I I 1 R2 N=N -N=N 1I(ois).. soil! 1) IIOJS(SO:) m-n -n11 l (5 ab- (5 3)(2ui)(D-U wherein R E, D, K, m, n and phave the significance The casting solution can also contain furtheraddiindicated, in accordance with one of the methods of tives forexample hardeners. sequestering agents and manufacture described above,and subsequently conwetting agents as well as sensitisers andstabilisers for densing the free amino group with one of the acid hathesilver halide. lides or anhydrides from which the radicals COX and Thedyestuffs neither undergo chemical reactions SO Y are derived. with thelight-sensitive materials nor significantly im- The dyestuffs of formulal may be used particularly pair their light-sensitivity.

advantageously in photographic materials as image The dyesutffs offormula (I) possess excellent resis dyestuffs for the silver dyestuffbleaching process. tance to diffusion, but also as well form stableaqueous Valuable photographic materials which contain at least solutionswhich are insensitive towards calcium ions, one layer having at leastone dyestuff of formula (I) on and can be bleached white withoutdifficulty. Thus they a layer support, can be manufactured in knownmanare significantly faster to light and diffusion than, for ner.example, the dyestuffs of the formula in particular, these dyestuffs Canbe pr in a mlllwherein R and Q each denotes any desired substituent,ti-layer material which contains on a layer support, a R, R" and Q eachdenotes a hydrogen atom or any layer which is dyed green-blue with a yeff 0f desired substituent and E, D, m, n, and p have the sigmula and isselectively nsi e, On p of this nificance indicated. The dyestuffs offormula 1) cause a layer dyed with a ag dyestuff. which is Selecneithera troublesome rise in viscosity on addition to tiv ly green-Sensitive,andfinally a layer y with a the casting solution nor any significantchange in visyellow dyestufi", which is selectively blue-sensitive. Thecosity h h ieady-to-cast mixture i l f to r r dye uff of formula y alsobe Present in The particular advantage of the dyestuffs of formulailiary layer or particularly in a layer adjacen to h (l)however residesin their extremely favourable speclight-sensitive layer. The extremelyadvantageous and m propel-flea Th i absorption maximum i l i not easilyobtained combination of numerous outstandi i h range of from 600 to 650nm so h i -fl ing properties in one molecule which is realised in the lh can b bi d i h a i bl magenta dyestuffs of formula l) becomesparticularly apparent tuff and an appropriate yellow dyestuff to form atriple when they are used as dyestuffs for images for direct dyestuffcombination which has significantly more adviewing. Furthermore thedyestuffs Of formula (1 C811 vantageous properties as regards exposuremetamerism also be used for retouching purposeswhen compared withmaterials containing other cyan In most cases it suffices to add thedyestuffs to be d ffg Furthermore, grey shades which appear usedaccording to the invention as a solution in water m l to h eye can b b id over h entire d i or in a solvent which is miscible with water to anaquerange. ous gelatine solution at normal or slightly elevated tem- Thedyestuffs of formula (1) have particularly low perature with good Stirg. Thereafter, Where PP subsidiary colour densities in the green andblue specpriate, this mixture is br g together with gelatine t ialregion and a low transmission in the red spectral containing silverhalide and/or other materials for the region. The flanks of theabsorption curves are exproduction of photographic images, cast o t abtremely steep, particularly towards the shorter wavestrate in the usualmanner to give a layer, and dried, if eng snecessary.

The dyestuff solution can also be added directly to MANUFACTURINGINSTRUCTIONS gelatine containing silver halide and/or other materials ne ns r t Ma ufacture of l-Acylaminofor the production of photographicimages. Thus for -hy r Xyn p h l n isulph0ni ac ds example the dyestuffsolution may be added only just 5 g o 78- percent 1-amin08- beforecasting. hydroxynaphthalene-3,6-disulphonic acid are sus- Instead ofsimple stirring, the usual methods of distripended in 500 ml f Wat r anddissolved at a pH value bution by means of kneading and/or shear forcesor ulof 7.5 by adding 40% sodium hydroxide solution. The

solution is heated to 40 to 50C and a total of 88 g of3-nitro-4-chlorobenzoyl chloride is added in portions of 2 to 3 g withgood stirring, the pH value of the solution being maintained at between6 and 7.5 by a dropwise addition of 40 percent sodium hydroxidesolution. The mixture is stirred for a further 2 hours at the sametemperature, heated to 60 to 70C, acidified with 37 percent hydrochloricacid to pH 2, and the reaction product precipitated with 300 ml ofethanol. After cooling, the yellowish crystals are filtered and theproduct is washed with a little ethanol. For further purification, theproduct is dissolved in 300 ml of water by heating to 80C and againprecipitated with 300 ml of ethanol. The misture is allowed to cool andthe crystals are filtered, washed with ethanol and dried in vacuo at 60Cand 150 mm Hg. Yield: 75 g of 1-(4'-chloro-3-nitrobenzoylamino)-8-hydroxynaphthalene-3,tS-disulphonic acid. The thin layer chromatogramindicates a single substance. The infra-red and nuclear resonancespectrum is in agreement with the requisite structure.

lb. 19.1 g of 83.7 percent l-amino-S- hydroxynaphthalene-3,6-disulphonicacid are suspended in 50 ml of N-methyl-pyrrolidone and 50 ml ofpyridine (dried over sodium sulphate) at 60C by means of good stirring,and treated in portions during one hour with 26 g of 4-methoxybenzoylchloride, provision being made by means of an oil bath for thetemperature to rise to 90C towards the end of the addition. The mixtureis left to react at this temperature for 2 hours, cooled to 60C andstirred for a further 3 hours. After cooling, the solvent and the excess4- methoxybenzoyl chloride are extracted from the reaction mixture withether, the oily residue is dissolved in 30 ml of water and treated with37 percent hydrochloric acid until pH 1 is reached, and the reactionmixture is precipitated with saturated sodium chloride solution. Afterstanding for 12 hours, the produce is filtered, crystallised from alittle ethanol/water (2:1) and dried in vacuo at 60C and 150 mm Hg.Yield: g of l-(4'-methoxybenzoylamino)-8-hydroxynaphthalene-3,6-disulphonic acid. The chromatogram indicates asingle substance. The infra-red andnuclear resonance spectra are inagreement with the requisite structure.

The l-acylamino-8-hydroxynaphthalene-3,6- disulphonic acids of thefollowing formulae can also be manufactured according to instruction la)I no sm4o n 01-6-0 II-HN HzNSOz CIIaNII SO;

SOaH

o c in o (HM (l (PO-"CONN 11 Hols -s H I o,N coHN )11 1103s SO1HllOOC(Cll CONll-OCOHN on 1103ssmu 011300- 0 OHN OH HOaS-SO3H HOOCCHCHCONI-L-O-CONI? (|)H 16 The l-acylamino-8-hydroxynaphthalene-3,6-disulphonic acids of the following formulae can be obtained according toinstruction lb) (1'24) B CO-HN )11 H038 SO3H 113c-d-c0-1n-: 311

Had

H 5 SO;H

1.2a) (EH10 Q-CO-HN on |I0,s- H01" O uoqm 011 HO3S[ I LSOaH COHN OH N l1.29 CO-HN OH HO3S@SO3H 1.30 N/ COHN 011 new -s01u lc. 31.9 g ofl-amino-8-naphthol-3,-disulphonic acid are dissolved in 300 ml of waterat pH 7.0, 16.4 g of anhydrous sodium acetate are added and the solutionis mixed with 16.7 ml of 3-trifluoromethylbenzoyl fluoride during 15minutes under reflux and whilst stirring. After 30 minutes a further16.7 ml of 3-trifluoromethylbenzoyl fluoride are added, the pH value isadjusted to 10.0 with sodium carbonate, the mixture is heated underreflux for 30 minutes, and the pH value is finally adjusted to 4.5 byaddition of 37 percent hydrochloric acid. The resulting precipitate isfiltered anddried. The product-of the formula HOaS SOal[ is obtained invery good yield. The compound of the formula (MN-O 0-111 on 11033 -SOzHis obtained in a similar manner.

2. Instruction for the Manufacture of Aminomonoazo Dyestuffs 24.8 g of2,5-dimethoxy-4-nitroaniline are emulsified in 50 ml of waterand 2.5 mlof a 1 percent solution of a condensation product of 1 mol ofp-tert.-octylphenol and 8 mols of ethylene oxide by stirring for 30minutes at 20C. 45 ml of 37 percent hydrochloric acid are run in withintensive external cooling (in order not to disturb the finedistribution), so that the temperature does not rise above 5C, and 32.8ml of 4 N sodium nitrite solution are added all at once, care beingtaken that the temperature does not exceed 7 to 8C by adding lumps ofice. A clear diazo solution is obtained within 30 minutes and isfiltered to remove constituents which are still solid.

In the meantime, 83 g of l-(4'-chlorobenzoylamino)-8-hydroxynaphthalene-3,6-disulphonic acid of formula (1.2) are dissolvedin 400 ml of water and the pH value is adjusted to 7.2 with 40 percentsodium hydroxide solution. 60 g of sodium tetraborate are added withgood stirring, the pH value is raised to 10.2 by means of 40 ml of 40percent sodium hydroxide solution, and the solution is cooled to 5 to 6Cby adding lumps of ice.

The above diazo solution is run in a thin stream into the solution ofthe coupling component, and the whole -is stirred for a further hour.Thereafter the reaction mixture is treated with 310 ml of 1 molar sodiumsulphide solution and the nitroazo dyestuff is reduced to the amino-azodyestuff at 40C and a pH value of 10 to l 1. After 5 hours the reductionis complete (recognisable from the single blue spot on thechromatogram). The pH value of the solution is reduced to 7.5 with 37percent hydrochloric acid, whereupon the dyestuff precipitates in aneasily filtrable form. The product is filtered and washed with 20percent sodium chloride solution until the filtrate is only pale yellow.in order to free the dyestuff from the sulphur which has separated, thefilter cake is dissolved in 2 litres of water, the solution is heated to90 to 95C, and the sulphur which has separated out is filtered. Thedyestuff is obtained from the filtrate by precipitation with saturatedsodium chloride solution. Yield: 72 g of the dyestuff of the formulaCl-O-CO-HN pH OCH;

The chromatogram shows a single spot.

The aminoazo dyestuffs of the following formulae can be manufactured ina similar manner 0100 O-HN c1 -N=N H038 -SO;H OCH:

O-co-my (|)H OCH;

N=N N11 l Hots s0.n 0cm i l 01 N:N NH;

Hols -so,H 0 CH:

OH 0 CH;

:3 SO H (BCH:

Q0 0-111? 0H ocn;

F, N=N Nu,

nois so,H OCH:

O-sm-m OH N=N NH:

1101s SO;H 0 CH:

30 o-rny on CH3 N=N- NH;

rims SO;II 0cm (2.10) Ol-OCO-HN 011 N=N NH:

HOaS- SO H 011,c11,o11

C -SOZHN on N=N NH,

H038 -so311 o-omcmon 01 C1C -COHIII (1)11 CH3 -N=N N11a 1101s SO3H 11100\(m -1|N on (mm,

-N N-- -Nn,

' N=N NH] HO3S S0311 11.00

C -c0 mf )11 002115 N=N -N11,

-s0.H H5020 IIOzS- S0311 11,0,(1

Goo-+111 111 qom -N=N NH;

(11 l c1- co-111 1 on 00111 N=N NH1 110.s -so.11 1130i) 3. Instructionsfor the Manufacture of Dyestuffs of Formula (1 3a. g of the aminoazodyestuff of formula (2.3) are dissolved in the form of the sodium saltin 900 ml of water, mixed with 80 ml of a naphthalene sulphonic acidsolution ml contain 1/10 mol of naphthalenel-sulphonic acid and 1/10 molof sulphuric acid, representing a total of 3/ 10 equivalents of acid).The mixture is cooled to 0C and diazotised by adding 18.4 ml of 4 Nsodium nitrite solution all at once. The reaction is allowed to proceedfor 45 minutes at 0 to 5C whilst stirring, the slight excess of nitrousacid is removed with a few drops of sulphamic acid, and the diazosolution is allowed to run at 0 to 5C within 15 minutes into a solutionof 70 g of the compound of formula (1.33) in 250 ml of water, 250 ml ofpyridine and 1 ml of 24 percent ammonia. During the addition of thediazo solution the pH value is kept between 9.5 and 10. The mixture isstirred for 1 hour at 20C, heated to 70C, and the dyestuff precipitatedfrom the hot solution with hot ethanol and filtered while still hot. Thefilter cake is washed with hot ethanol until the initially reddishfiltrate runs colourless. For further purification, the residue isdissolved in 1 litre of water at 70C and the dyestuff is againprecipitated with hot ethanol with the addition of a few drops of 7 Npotassium acetate solution.

The product is filtered hot and washed with hot ethanol until thefiltrate runs colourless. The residue is dried in vacuo at 60C/l50 mmHg. I Yield: 42.1 g of the dyestuff of formula (101) of Table I.

3b. A diazo solution manufactured according to instruction 30) from 3.5g of the aminoazo dyestuff of formula (2.4) is run during 10 minutes at0 to 5C into a solution of 4 g of the 1-amino-8-naphtho1 derivative offormula (1.8) in 50 ml of water, 60 ml of pyridine and 4 ml of 24percent ammonia. The pH value during coupling should be between 9 and9.5. The mixture is stirred for one hour at 20C, heated to 70C, and thedyestufi precipitated with hot ethanol. The further purification of thedyestuff is carried out according to instruction 3a).

Yield: 3.1 g of the dyestuff of formula (103). The chromatogramindicates a single substance.

The dyestuffs (101 (102), (104) to (121 to (149), (152) to (155) ofTable 1 can also be manufactured according to instructions 3a) and 3b).

3c. 4.85 g of the aminoazo dyestuff of formula (2.7) are dissolved inthe form of the sodium slat in 100 ml of water, mixed with 5 ml of anaphthalene sulphonic acid solution (100 ml of this solution contain 1/10 mol of naphthalene-l-sulphonic acid and 1/ 10 mol of sulphuric acid,that is to say a total of 3/10 equivalents of acid) and diazotised with1.4 ml of 4 N sodium nitrite solution at 5C.

The mixture is allowed to react for one hour at 5C whilst stirring andthereafter the excess sodium nitrite is destroyed by adding therequisite amount of sulphamic acid. The diazo solution is added at 15Cto a solution of 1 1.6 g of the compound of formula (1.31) and 1 g ofsodium tetraborate in 50 ml of water and 15 ml of pyridine. The pH valueis kept at 9.7 during the entire coupling by adding 5 N sodium carbonatesolution. After one hour the dyestuff which has separated is filteredand purified by recrystallisation from dimethylformamide/water 1 :1 Thecompound of formula (122) of the Dyestuff Table l hereafter is obtainedin good yield, and in acceptable quality according to a thin layerchromatogram, as a dark blue powder.

The dyestuffs of formulae (123) and (124) may be obtained in a similarmanner. The dyestuffs of formulae (125) to (129), (150) and (151) may besimilarly obtained from the compounds of formulae (1.2), (13), (1.32)and (1.33).

Table 1 below characterises the dyestuffs of formulae (101) to (155).The symbols R 12,, D, E and K represent radicals in the formula 5 theabsorptions maximum in nm, in which column 11a gives the value measuredin dimethylformamide/water, 1:1, and column 11b the value measured ingelatine. 1n the dyestuff of formula (141) the sulphonic acid groups inthe right-hand side naphthalene radical of formula 10 (24) are in the3,5-position instead of the 3,6-positi0n.

155 4-COOCH H 1 111 m D E K Q iia i1 l 142 4-c 011 11 410113 --0 c111660+72u 02:1

143 4-NHC 0 cmcmc 0 011 H o 0113 0 0111 O 677+738 633 144 H OCH -oc11 c12 WHC 1 3 i e14+1s0 6 1 145 3-SO2NHz H 0 CH; -0 CH3 N 660+607 s 146 401II 0 CH; -0 CH3 s7e+r2o 621 c 0 SOgNH2.

141 e0 OH; H --0 0113 o 011; 1 s11+734 634 14s 4-t-Butyl u -0 cm -0 on;1 s15+134 e27 149 H -OCH -OCH Cl I M O a 3 I e1s+1ss 613 150 4-01 II-H;C 0 CH: 642+700 580+ 3 151 4-N02 11 11 -0 cmcmon s 0 632+678 eas+soen -0c11 -0cn 6'2 19 152 4-NHS 02-90113 3 a -c 0C s0:cm

153 4-NHCO(CHZ)1COOH 11 -0c11 0c113 c1 e1o+122 .1

154 4-NHCOCH=CIICOOH 11 -0c11 1 oc1r s ONH- e14+125 I 1 r@ "G -0c11;-0c113 Q 676+736 e EXAMPLE 1 0.5 ml of a 1 percent aqueous solution ofthe cyan dyestuff of formula (106) and 3.3 ml of silver bromide emulsionwhich contains g of silver per litre are pipetted into a test tube andmade up to 10.0 ml with deionised water. This solution is vigorouslymixed and kept for 5 minutes at C in a water bath. The casting solutionat 40C is cast onto a substrated glass plate size 13 cm. 1 8 cm. Aftersolidifying at 10C, the plate is dried in a drying cabinet withcirculating air at 32C. A strip cut to 3.5 cm.l8cm is exposed for 3seconds with Luitlcm under a step wedge through a Kodak 2b 49 bluefilter. Thereafter the process is continued as 50 follows:

1. 7 minutes development in a bath which contains per litre 20 g ofanhydrous sodium sulphite, l g of 4-methylaminophenol sulphate, 4 g ofhydroquinone, 10 g of anhydrous sodium carbonate and 2 g of potassiumbromide;

3. 2% minutes soaking;

4. 8 minutes colour bleaching in a bath which contains per litre ml of37 percent hydrochloric acid, 50 g of potassium bromide, g of thiourea,5 mg of colour bleaching catalyst of the formula NHz 27 28 and 20 ml ofa mixture of 500 ml of diethylene glycol 5. 3 to l2 minutes colourbleaching with a solution and 500 ml of water; which contains per litreof water 50 to 80 g of po- 5. 2 minutes soaking; tassium bromide, 40 to80 g of thiourea, 35 to 80 6. 8 minutes bleaching of residual silver ina bath g of 30 percent sulphuric acid and 0.001 to 0.01 g which containsper litre 100 ml of 37 percent hyof the colour bleaching catalyst offormula (26); drochloric acid, 50 g of crystalline copper sulphate 6.minutes soaking; and 45 of potassium ofpotassium bromide; 7. 5 minutesbleaching of residual silver with a solu- 7. 2 minutes soaking; tion of60 g of a crystalline copper sulphate, 80 g 8. 4 minutes fixing asindicated under 2.; of potassium bromide and ml of 30 percent hy- 9. 10minutes soaking. 10 drochloric acid per litre of water; A brilliantblue-green wedge very fast to light is ob- 8. 5 minutes soaking; tainedwhich is bleached completely white in the posi- 9. 5 minutes fixing asindicated under 3.; tion of the originally greatest silver density. 10.5 minutes soaking.

Similar results are obtained when a different dyestuff A light-stable,document-fast positive viewing image of Table I is used instead of thedyestuff of formula 15 iS Obtained- (l06). Similar results are obtainedwhen another dyestuff EXAMPLE 2 )Table I IS used instead of the dyestuffof formula Th r 11 1 e o owing ayers are successively applied to anEXAMPLE 3 opaque white acetate film provided with an adhesive layer: 3.3ml of a 6 percent gelatine solution, 2.0 ml of a l l. Red-sensitivesilver bromide emulsion in gelatine, percent aqueous solution of thehardener of formula containing the cyan dyestuff of formula (I01). and0.5 ml of a l percent aqueous solution of the 2. Colourless gelatinelayer without silver halide. cyan dyestuff of formula (102) are pipettedinto a test 3. Green-sensitive silver bromide emulsion in gela- 25 tubeand made up to 10.0 ml with deionised water. The tine, containing themagenta dyestuff of th f whole is thoroughly mixed and kept for 5minutes at mula 40C in a water bath. The casting solution at 40C is (21)HOaIS SOaH OH HO N=N-NI[O CNHC O-lIN-O c-1IN N=N- 112w 110w; s onr NH,

4. Blue-sensitive silver bromide emulsion in gelatine cast onto asubstrated glass plate size 13 cm.l8 cm.

containing the yellow dyestuff of the formula After solidification at10C, the plate is dried in a dry- .(28) ,2... 1103 8 H3O (|:H, $0.11

s olri v H0=s The "gelatine layers can further contain additives for ingcabinet with circulating air at 32C. example wetting agents, hardenersand stabilisers for A mixture of 3.3 ml of a 6 percent gelatinesolution, the silver halide. In other respects the procedure fol- 50 2.0ml of 1 percent aqueous solution of the hardener of lowed is such thatthe individual layers contain per formula (25), 3.3 ml of silver bromideemulsion consquare metre 0.5 g of the particular dyestuff and an taining35 g of silver per litre, and 1.4 ml of deionised amount of silverbromide corresponding to l to 1.2 g water is then applied to the driedlayer at 40C. The of silver. whole is allowed to solidify and dry asindicated above.

A strip, cut to 3.5 cm.l8 cm, is exposed for 10 seconds with Lux/cmunder a step wedge through a Kodak 2b 49 blue filter. Thereafter theprocedure described in Example 1 is followed but instead of the colourbleaching catalyst of formula (26) the colour 1. 6 minutes developmentin a bath which contains bl hin catalyst of the formula per litre ofwater 50 g of anhydrous sodium sul- This film is exposed to red, greenand blue copying 55 light under a coloured diapositive. Thereafter thecopy is developed in accordance with the following instruction:

phite, 0.2 g of l-phenyl-3-pyrazolidone, 6 g of hy- (29) N CH;droquinone, 35 g of anhydrous sodium carbonate, 4 g of potassium bromideand 0.3 g of benztriazole; 2. 5 minutes soaking; N CH; 3. 6 minutesfixing in a solution of 200 g of crystalline sodium thiosulphate and 20g of potassium metabiis used. A brilliant, blue-green wedge very fast tolight sulphite in 1 litre of water; is obtained which is bleachedcompletely white in the 4. 5 minutes soaking; area of the originallygreatest silver density.

Similar results are obtained when one of the other dyestuffs of Table lis used instead of the dyestuff of formula (102).

EXAMPLE 4 per litre 1 g of p-methylaminophenol sulphate, 20

g of anhydrous sodium sulphite, 4 g of hydroquinone, 10 g of anhydroussodium carbonate, 2 g of potassium bromide and 3 g of sodiumthiocyanate; 2. 2 minutes soaking;

Y represents a lower alkyl or a phenyl, alkylphenyl or HOOC-phenylgroup, Z represent a hydroxyl, lower alkyl, phenyl amino or alkylaminogroup and W represents a lower alkyl or alkoxy group, or a hydroxyl,phenyl or unsubstituted amino group, R denotes a hydrogen atom or hasthe significance indicated for R,, R, and R, being in the 3-, 4- or5-positions to the CO- group, D and E independently of one another eachdenotes a hydrogen or chlorine atom or a methyl, methoxy, ethoxy orhydroxyethoxy group, K denotes an acyl radical of an aliphatic oraromatic carboxylic or sulphonic acid, or of a heterocyclic carboxylicacid, and m, n and p each equals 1 or 2.

2. Photographic light-sensitive material as claimed in I 3. 2 minutestreatment in a reversal bath which conclaim 1, that contains a dyestuffof the formula tains per litre 5 g of potassium bichromate and 5 ml of96 percent sulphuric acid;

4. 4 minutes soaking;

5. 5 minutes treatment in a bath which contains 50 g of anhydrous sodiumsulphite per litre;

6. 3 minutes soaking;

7. 4 minutes development in a bath which contains per litre 2 g of1-phenyl-3-pyrazolidone, 50 g of anhydrous sodium carbonate, 2 g ofsodium hexametaphosphate and 20 ml of a 1 percent aqueous solution oftert.-butylaminoborane;

8. 2 minutes soaking;

9. further treatment as indicated in Example 1 under A brilliant,blue-green wedge very fast to light running counter to the original usedis obtained.

HO HN K in which R, denotes a hydrogen or halogen atom or a nitro group,R denotes a halogen atom, a nitro, cyano, trifluoromethyl, lower alkylor alkoxy group or a radical of the formula NHCOX,, -NH-SO Y,, SO,-Z, orCOW,, in which X, represents an HOOC-alkyl, HOOC-alkenyl, HOOC-phenyl orphenyl group, Y, represents a lower alkyl or alkylphenyl group or aphenyl group, Z, represents a lower alkyl, phenyl amino or alkylaminogroup and W, represents a lower alkyl or alkoxy group or a phenyl orhydroxyl group, D, and E, independently of one another each denotes amethyl, methoxy, ethoxy or hydroxy-ethoxy group and K, m, n and p havethe significance indicated in claim 1, and R, and R, are in the 3-, 4-or 5-positions to the -C0 group.

3. Photographic light-sensitive material which con- Similar results areobtained when using one of the tains, on a support in at least one layerat least one dyeother dyestuffs of Table I.

We claim:

1. Photographic light-sensitive material that contains on a support inat least one layer containing silver halide a dyestuff of the formula inwhich R, denotes a halogen atom, a nitro, cyano, trifluoromethyl, loweralkyl or alkoxy group or a radical of the formula --NH--CO-X, SO Z or-CO--W, in which X represents a hydroxyl, HOOC-alkyl, HOOC-alkenyl,HOOC-phenyl, HO S phenyl, phenyl, furyl, thienyl or pyridyl group,

stuff of the formula l 02-11 slwmxwn in which R, denotes a halogen atom,a nitro, trifluoromethyl, lower alkyl or alkoxy group, or a radical ofthe formula NH--COX, -NHSO -Y, -SO Z or -COW,, in which X represents ahydroxyl,

HOOC-alkyl, HOOC-alkenyl, HOOC-phenyl, H0 8- phenyl, phenyl, furyl,thienyl or pyridyl group, Y represents a lower alkyl or a phenyl,alkylphenyl or HOOC- phenyl group and Z represents a hydroxyl, loweralkyl amino or alkylamino group, W, represents a lower alkyl or alkoxygroup or a phenyl or a hydroxyl group, R,

31 denotes a hydrogen atom or has the significance indicated for R R andR being in the 3-, 4- or 5-positions to the CO group, D and Eindependently of one another each denotes a hydrogen or chlorine atom ora Q4: OHN on methyl, methoxy, ethoxy or hydroxyethoxy group, K denotesan acyl radical of an aliphatic or aromatic carboxylic or sulphonic acidor of a heterocyclic carboxylic acid, and m, n and p each equals 1 or 2.

4. Photographic material according to claim 3, that contains a dyestuffof the formula X. Ra

in which R R K, m and n have the significance indicated in claim 3 and Dand E independently are methyl, methoxy, ethoxy or hydroxyethoxy.

5. Photographic material as claimed in claim 2 that contains a dyestuffof the formula 15 moyl,

32 in which R R and K have the significance indicated in claim 3.

7. Photographic material as claimed in claim 5, that contains at leastone dyestuff of the formula S0 11 CH3 110 s SOall in which K, denotesthe acyl radical of an alkanecarboxylic acid, benzoic acid, benzoic acidsubstituted by halogen, nitro, alkyl, CF acetylamino, CH O,sulphamethylsulphamoyl, methoxycarbonyl, HOOC-alkylene-carbonyl,fumaroyl, benzenesulphonylamino, tosylamino and methylsulphonylamino,

pyridine carboxylic acid or unsubstituted benzene sulphonic acid, and Rand R have the significance indicated in claim 5.

8. Photographic material as claimed in claim 5, that contains at leastone dyestuff of the formula lower alkyl, phenyl, alkylphenyl, orHOOC-phenyl.

6. Photographic material as claimed in claim 3 that contains at leastone dyestuff of the formula 5 -COHN OH OCH; HO l l 1 Re I H0 8 SO3H OCH:HOgS in which K2 denotes the acyl radical of a benzene carboxylic acidwhich may be substituted by an alkylsulphone group which contain at most5 carbon atoms, a halogen atom or a nitro, trifluoromethyl oramidosulphone group or the radical of a benzene sulphonic acid orpyridine carboxylic acid, and R and R have the significance indicated inclaim 5.

9. Photographic material as claimed in claim 1 that contains at leastone dyestuff of the formula 33 34 in which R denotes a chlorine orbromine atom or a in which G denotes a hydrogen or chlorine atom andnitro, trifluoromethyl, H N-SO H C-N- 6,, denotes a hydrogen or chlorineatom or an H SO H C-SO H CSO NH, H N-SO -group, R denotes a chlorineatom, a nitro H C SO .NH or an H NSO, group, and R, has the significanceV g n V M i 5 indicated in claim 9.

H so i 12. Photographic material as claimed in claim 1, that a 2contains a dyestuff of the formula H C CO-NH-, HOOC(Cl-l -CO--NH,

5% 4: 0-HN OH 0cm HO NII-K I I l l R,

1103s SO3H $0113 H035 -s0,-,n

HOOC-(CH2)3CONH-, HOOCCH=)\ CH CO NH HOOC H3CO in which R represents achlorine or bromine atom or a cyano, nitro, trifluoromethyl, H,NSO,,H,C-N-

and R denotes a hydrogen or chlorine atom, the radicals R and R being inthe 3- and 4-positions to the H 0 \TH --CO group, and K represents theacyl radical of 25 a 2 pyridine-3-carboxylic acid or of a benzenecarboxylic acid of the formula m which G denotes a hydrogen or halogenatom and G denotes a hydrogen or halogen atom or a nitro,trifluoromethyl or Z -SO,- group, in which Z 35 represents a lower alkylgroup or unsubstituted amino 7 7 group nooccomr cup,

l0. Photographic material as claimed in claim 9 that contains at leastone dyestuff of the formula ;2 COHN on OCH: Hp ITH-Ki Re in which Krepresents the acyl radical of pyridine-3- R represents 3 nitro group ora hydrogen or chlorine carboxylic acid or of a benzene carboxylic acidof the a om and K3 represents the acyl radical of pyridine-3- formula v50 carboxylic acid, benzene sulphonic acid or a benzene carboxylic acidof the formula in which G denotes a hydrogen atom or chlorine atom and0,, denotes a hydrogen or chlorine atom or a nitro, trifluoromethyl or HNSO group, and R and R have the significance indic t d i l i 9, in whichG, denotes a hydrogen or chlorine atom, and

1 l. Photographic material as claimed in claim 9, that 0 2' denotes ahydr gen r Chlorine atom or a nitro, tricontains at least one dyestuffof the formula fluommethyl, a 2 2 zg p- V G: 5% -co-1-rN OH OCH; HO NH-Co m 1 l l l 1 G5 --N=N- N=N HOaS SOaH OCH; HOQS SOaH 13. Photographicmaterial as claimed in claim ill that 15. Photographic material asclaimed in claim 1 that contains a dyestuff of the formula contains atleast one dyestuff of the formula Rn G3 OOI-IN 01-1 00113 no NIICO 2 I XR Ga Hols SO;,H ()CH; 1103s SO:4H

HzNOzSOCO-HYII on (1)0113 ml) IIIHCO- N=N N=N H038 SO3H 0 CH3 H0 8SO3I'I wherein R G and 6,, have the significance indicated 16.PHotographic material as claimed in claim 1 that in claim 11 and Rdenotes a chlorine or bromine contains at least one dyestuff of theformula atom or a nitro, H NSO H CSO H COOC,

H CSO -NH- or NC 17. Photographic material as claimed in claim 1 that14. Photographic material as claimed in claim 1 that contains at leastone dyestuff of the formula contains at least one dyestuff of theformula

2. Photographic light-sensitive material as claimed in claim 1, thatcontains a dyestuff of the formula
 3. Photographic light-sensitivematerial which contains, on a support in at least one layer at least onedyestuff of the formula
 4. Photographic material according to claim 3,that contains a dyestuff of the formula
 5. Photographic material asclaimed in claim 2 that contains a dyestuff of the formula 6.Photographic material as claimed in claim 3 that contains at least onedyestuff of the formula
 7. Photographic material as claimed in claim 5,that contains at least one dyestuff of the formula
 8. Photographicmaterial as claimed in claim 5, that contains at least one dyestuff ofthe Formula
 9. Photographic material as claimed in claim 1 that containsat least one dyestuff of the formula
 10. Photographic material asclaimed in claim 9 that contains at least one dyestuff of the formula11. Photographic material as claimed in claim 9, that contains at leastone dyestuff of the formula
 12. Photographic material as claimed inclaim 1, that contains a dyestuff of the formula
 13. Photographicmaterial as claimed in claim 11 that contains a dyestuff of the formula14. Photographic material as claimed in claim 1 that contains at leastone dyestuff of the formula
 15. Photographic material as claimed inclaim 1 that contains at least one dyestuff of the formula 16.PHotographic material as claimed in claim 1 that contains at least onedyestuff of the formula
 17. Photographic material as claimed in claim 1that contains at least one dyestuff of the formula